Water-soluble azo dyes containing diaminopyrimidine coupler components

ABSTRACT

Dyes having the formula: ##STR1## IN WHICH D is the radical of a diazo component; and 
     A is the radical of a pyrimidine coupling component bearing two unsubstituted or substituted amino groups as substituents. The dyes are eminently suitable for dyeing natural and synthetic polyamides; brilliant colorations are obtained.

This application is a continuation-in-part of our copending application Ser. No. 434,248 (now abandoned).

The invention relates to dyes which in the form of the free acid correspond to the formula (I): ##STR2## in which

D is the radical of a diazo component; n is one of the integers 1, 2 and 3; A is a radical of the formula (IIa) or (IIb): ##STR3##

Z is hydrogen or unsubstituted or substituted alkyl, cycloalkyl, aralkyl or aryl; and

Z¹, Z², Z³ and Z⁴ independently of one another may be hydrogen or unsubstituted or substituted alkyl, cycloalkyl, polycycloalkyl, aralkyl or aryl.

One of the radicals Z¹ to Z⁴ is preferably other than hydrogen.

The invention relates particularly to dyes of the formula (III): ##STR4## in which

D and n have the above meanings and

A¹ is a radical of the formula (IVa) of (IVb): ##STR5##

B is hydrogen, alkyl, alkyl bearing hydroxy, alkoxy, alkanoyloxy or phenoxy as a substituent, aralkyl, cycloalkyl, phenyl or phenyl bearing alkyl, halogen, nitro, cyano, alkoxycarbonyl, carbamoyl or sulfamoyl as a substituent;

R is hydrogen, alkyl of one to eight carbon atoms which may be interrupted by oxygen atoms and which may bear hydroxy, acyloxy, alkoxy, cyano, cycloalkoxy, aralkoxy or aroxy as a substituent, cycloalkyl or polycycloalkyl of five to fifteen carbon atoms which may bear hydroxy, chloro, hydroxyalkyl, chloroalkyl or alkyl as a substituent, aralkyl of seven to fifteen carbon atoms, phenyl, phenyl bearing chloro, hydroxy, alkoxy, alkyl, hydroxyalkyl or hydroxyalkoxy as a substituent, alkenyl, pyrrolidonylalkyl or carboxyalkyl;

R¹ is hydrogen, alkyl of one to eight carbon atoms or hydroxyalkyl of two to nine carbon atoms;

R and R¹ with the nitrogen may be the radical of pyrrolidine, piperidine or morpholine; and, independently of each other,

R² may have the same meaning as R;

R³ may have the same meaning as R¹ ; and

R² and R³ together may have the same meaning as R and R¹ together;

and in which the radical D and/or the substituents B and R to R³ may contain sulfonic acid groups.

The radical D of the diazo component may be derived particularly from aniline, aminophthalimide and aminoazobenzene derivatives and these may bear for example hydroxysulfonyl, halogen, hydroxy, alkyl, alkoxy, acylamino, cyano, alkylsulfone, phenylsulfone, nitro, carboxyl, carbalkoxy, carbamoyl, N-substituted carbamoyl, sulfamoyl, N-substituted sulfamoyl or benzothiazolyl.

Examples of individual substituents, in addition to those already mentioned, are: chloro, bromo, methyl, ethyl, trifluoromethyl, methoxy, ethoxy, methylsulfonyl, ethylsulfonyl, carbomethoxy, carboethoxy, carbo-β-ethoxyethoxy, carbo-β-methoxyethoxy, carbobutoxy, carbo-β-butoxyethoxy, N-methylcarbamoyl, N-ethylcarbamoyl, N-butylcarbamoyl, N-hexylcarbamoyl, N-β-ethylhexylcarbamoyl, N-β-hydroxyethylcarbamoyl, N-β-methoxyethylcarbamoyl, N-γ-methoxypropylcarbamoyl, N,N-dimethylcarbamoyl, N,N-diethylcarbamoyl, N-methyl-N-β-hydroxyethylcarbamoyl, N-phenylcarbamoyl, carboxylic acid piperidide, morpholide or pyrrolidide and the corresponding sulfonamides, acetylamino, propionylamino, butyrylamino, methylsulfonylamino, phenylsulfonylamino, hydroxyacetylamino, benzoylamino, p-chlorobenzoylamino, phenylacetylamino and the radicals of the formulae ##STR6##

Examples of radicals Z or B (other than hydrogen) are: alkyl of one to seven carbon atoms, methoxyethyl, ethoxyethyl, phenoxyethyl, benzyl, phenylethyl, 1-phenylpropyl, cyclohexyl, phenyl, methylphenyl, chlorophenyl, methoxyphenyl, ethoxyphenyl, nitrophenyl, carbamoylphenyl or sulfamoylphenyl. The amide groups may also be N-monosubstituted or N,N-disubstituted and examples of such substituents are alkyl (--CH₃, --C₂ H₅, --C₄ H₉), cyclohexyl or phenyl.

The following radicals are also suitable: ##STR7##

Preferred examples of radical B are: hydrogen, methyl, ethyl, propyl, butyl, α-ethylpentyl, benzyl, phenylethyl, phenyl which may bear methyl, ethyl, methoxy, ethoxy or chloro as substituents and the radicals of the formulae: ##STR8##

Specific examples of radicals Z¹ to Z⁴ and R to R³ (in addition to those already specified) are:

(1) optionally substituted alkyl: CH₃, C₂ H₅, n--C₃ H₇, i--C₃ H₇, n--C₄ H₉, i--C₄ H₉, C₆ H₁₃, ##STR9## CH₂ CH₂ OH, (CH₂)₃ OH, ##STR10## (CH₂)₄ OH (CH₂)₆ OH, ##STR11## (CH₂)₂ O(CH₂)₂ OH, (CH₂)₃ O(CH₂)₄ OH, (CH₂)₃ OC₂ H₄ OH, (CH₂)₃ OC₂ H₄ OCH₃, (CH₂)₃ OC₂ H₄ OC₂ H₅, (CH₂)₃ O(CH₂)₆ OH, (CH)₃ OC₂ H₄ OCH(CH₃)₂, (CH₂)₃ OC₂ H₄ OC₄ H₉, (CH₂)₃ OC₂ H₄ OCH₂ C₆ H₅, (CH₂)₃ OC₂ H₄ OC₂ H₄ C₆ H₅, ##STR12## (CH₂)₃ OC₂ H₄ OC₆ H₅, ##STR13## the corresponding radicals in which the groupings: --OC₂ H₄ -- ##STR14## are present twice, three times or four times, CH₂ CH₂ OCH₃, CH₂ CH₂ OC₂ H₅, CH₂ CH₂ OC₃ H₇, CH₂ CH₂ OC₄ H₉, CH₂ CH₂ OC₆ H₅, (CH₂)₃ OCH₃, (CH₂)₃ OC₂ H₅, (CH₂)₃ OC₃ H₇, (CH₂)₃ OC₄ H₉, ##STR15## (CH₂)₃ OC₆ H₁₃, (CH₂)₃ OC₈ H₁₇, ##STR16## (CH₂)₃ OCH₂ C₆ H₅, (CH₂)₃ OC₂ H₄ C₆ H₅, (CH₂)₃ OC₆ H₅, ##STR17##

(2) optionally substituted cycloalkyl and polycycloalkyl: ##STR18##

(3) aralkyl: CH₂ C₆ H₅, C₂ H₄ C₆ H₅, ##STR19## and C₆ H₄ CH₃ instead of C₆ H₅.

(4) optionally substituted phenyl: C₆ H₅, C₆ H₄ CH₃, C₆ H₃ (CH₃)₂, C₆ H₄ OCH₃, C₆ H₄ OC₂ H₅, ##STR20## C₄ H₄ OCH₂ CH₂ OH or C₆ H₄ Cl.

(5) CH₂ CH═CH₂, (CH₂)₂ COOH, (CH₂)₅ COOH and ##STR21## in which n is 2, 3, 4 or 6, C₂ H₄ OCOCH₃, C₂ H₄ OCHO, C₂ H₄ OCOCH₂ COCH₃, (C₂ H₄ O)₂ COOH₃, (C₂ H₄ O)₂ CHO, (CH₂)₃ OCOCH₃, (CH₂)₃ OCHO, C₂ H₄ OCOC₂ H₄ COOH.

Examples of radicals R to R³ containing sulfonic acid groups are (in addition to SO₃ H): CH₂ CH₂ SO₃ H, CH₂ CH₂ OSO₃ H, (CH₂)₃ OSO₃ H, ##STR22## (CH₂)₄ OSO₃ H, (CH₂)₆ OSO₃ H, ##STR23## (CH₂)₂ O(CH₂)₂ OSO₃ H, (CH₂)₃ O(CH₂)₂ OSO₃ H, (CH₂)₃ O(CH₂)₄ OSO₃ H, (CH₂)₃ OC₂ H₄ OCH₂ C₆ H₄ SO₃ H, (CH₂)₃ OC₂ H₄ OC₂ H₄ C₆ H₄ SO₃ H, (CH₂)₃ OC₂ H₄ OC₆ H₄ SO₃ H, CH₂ CH₂ OC₆ H₄ SO₃ H, (CH₂)₃ OC₆ H₄ SO₃ H, (CH₂)₃ OCH₂ C₆ H₄ SO₃ H, (CH₂)₃ OC₂ H₄ C₆ H₄ SO₃ H, ##STR24## CH₂ C₆ H₄ SO₃ H, C₂ H₄ C₆ H₄ SO₃ H, ##STR25##

Examples of substituents R to R³ which are preferred are: hydrogen, CH₃, C₂ H₅, n--C₃ H₇, i--C₃ H₇, n--C₄ H₉, i--C₄ H₉, C₆ H₁₃, CH₂ CH₂ OH, (CH₂)₃ OH, ##STR26## (CH₂)₄ OH, (CH₂)₆ OH, ##STR27## (CH₂)₂ O(CH₂)₂ OH, (CH₂)₃ O(CH₂)₂ OH, (CH₂)₃ O(CH₂)₄ OH, (CH₂)₃ O(CH₂)₆ OH, ##STR28## CH₂ CH₂ OCH₃, CH₂ CH₂ OC₂ H₅, CH₂ CH₂ OC₄ H₉, (CH₂)₃ OCH₃, (CH₂)₃ OC₂ H₅, (CH₂)₃ OC₃ H₇, (CH₂)₃ OC₄ H₉, (CH₂)₃ OC₆ H₁₃, (CH₂)₃ OC₈ H₁₇, ##STR29## (CH₂)₃ OC₂ H₄ OCH₃, (CH₂)₃ OC₂ H₄ OC₄ H₉, (CH₂)₃ OC₂ H₄ OC₆ H₅, ##STR30## CH₂ C₆ H₅, C₂ H₄ C₆ H₅, ##STR31## C₆ H₅, C₆ H₄ CH₃, C₆ H₃ (CH₃)₂, C₆ H₄ OCH₃, C₆ H₄ OC₂ H₅, C₆ H₄ OC₂ H₄ OH, C₆ H₄ Cl, CH₂ CH₂ SO₃ H, CH₂ CH₂ OSO₃ H, (CH₂)₃ OSO₃ H, ##STR32## (CH₂)₄ OSO₃ H, (CH₂)₆ OSO₃ H, (CH₂)₂ O(CH₂)₂ OSO₃ H, (CH₂)₃ O(CH₂)₂ OSO₃ H, (CH₂)₃ O(CH₂)₄ OSO₃ H, (CH₂)₃ O(CH₂)₆ OSO₃ H, (CH₂)₃ OC₆ H₄ SO₃ H, (CH₂)₃ OCH₂ C₆ H₄ SO₃ H, (CH₂)₃ OC₂ H₄ C₆ H₄ SO₃ H, CH₂ C₆ H₄ SO₃ H, C₂ H₄ C₆ H₄ SO₃ H, ##STR33##

Dyes are alo preferred in which two radicals R together with the nitrogen form the radical of pyrrolidine, piperidine or morpholine.

The dyes of formula (I) may be prepared or used in the form of the free acids or conveniently as water-soluble salts, for example as alkali metal, ammonium or substituted ammonium salts. Examples of substituted ammonium cations in the salts are trimethylammonium, methoxyethylammonium, hexoxypropylammonium or dimethylphenylbenzylammonium.

Dyes of formula (I) may be prepared by reacting a diazo compound of an amine of formula (V):

    d--nh.sub.2                                                (v)

with a coupling component of formula (VI):

    h--a                                                       (vi),

d and/or HA normally containing at least one sulfonic acid group. Diazotization and coupling are carried out by conventional methods. The new dyes, particularly those having sulfuric acid hemiester groups may also be obtained by first preparing the compounds devoid of SO₃ H groups and then converting these with a sulfonating agent such as concentrated sulfuric acid, sulfuric acid monohydrate or oleum into the dye of formula (I). The Examples may be referred to for details. Coupling components of the formula H--A and their production are known from German Laid Open Specification No. 22 02 820.

Examples of compounds of the formula (V) are: aniline, 2-chloroaniline, 3-chloroaniline, 4-chloroaniline, 2-bromoaniline, 3-bromoaniline, 4-bromoaniline, 2-nitroaniline, 3-nitroaniline, 4-nitroaniline, 2-toluidine, 3-toluidine, 4-toluidine, 2-cyanoaniline, 3-cyanoaniline, 4-cyanoaniline, 2,4-dicyanoaniline, 3,4-dichloroaniline, 2,5-dichloroaniline, 2,4,5-trichloroaniline, 2,4,6-trichloroaniline, 2-chloro-4-nitroaniline, 2-bromo-4-nitroaniline, 2-cyano-4-nitroaniline, 2-methylsulfonyl-4-nitroaniline, 4-chloro-2-nitroaniline, 4-methyl-2-nitroaniline, 2-methoxy-4-nitroaniline, 1-amino-2-trifluoromethyl-4-chlorobenzene, 2-chloro-5-aminobenzonitrile, 2-amino-5-chlorobenzonitrile, 1-amino-2-nitrobenzene-4-sulfonic acid n-butylamide or β-methoxyethylamide, 1-aminobenzene-4-methylsulfone, 1-amino-2,6-dibromobenzene-4-methylsulfone, 1-amino-2,6-dichlorobenzene-4-methylsulfone, the methyl, propyl, β-methoxyethyl or butyl ester of 3,5-dichloroanthranilic acid, the methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, or β-methoxyethyl ester of 3,5-dibromoanthranilic acid, N-acetyl-p-phenylenediamine, N-acetyl-m-phenylenediamine, N-benzenesulfonyl-p-phenylenediamine, 4-aminoacetophenone, 4-aminobenzophenone, 2-aminobenzophenone, 2-aminodiphenylsulfone, 4-aminodiphenylsulfone, the methyl, ethyl, propyl, butyl, isobutyl, β-methoxyethyl, β-ethoxyethyl, methyl diglycol, ethyl diglycol or methyl triglycol ester of 2-aminobenzoic acid or 3-aminobenzoic acid or 4-aminobenzoic acid, 3-aminophthalic acid, 4-aminophthalic acid, the dimethyl, diethyl, dipropyl or dibutyl ester of 5-aminoisophthalic or aminoterephthalic acid, the amide, methylamide, propylamide, butylamide, isobutylamide, cyclohexylamide, β-ethylhexylamide or γ-methoxypropylamide of 3-aminobenzoic acid or 4-aminobenzoic acid, the dimethylamide, diethylamide, pyrrolidide or morpholide of 2-aminobenzoic acid, 3-aminobenzoic acid or 4-aminobenzoic acid, the diamide of 5-aminoisophthalic acid, the imide, β-hydroxyethylimide, methylimide, ethylimide or tolylimide of 3-aminophthalic acid or 4-aminophthalic acid, the dimethylamide, diethylamide, pyrrolidide or morpholide of 4-aminobenzenesulfonic acid, the hydrazide of 3-aminophthalic acid or 4-aminophthalic acid, the ethylimide, butylimide or methoxyethylimide or 4-aminonaphthalic acid, 1-aminoanthraquinone, 4-aminodiphenylene oxide, 2-aminobenzothiazole, 4-nitronaphthylamine, 5-nitronaphthylamine, 4-aminoazobenzene, 2',3-dimethyl-4-aminoazobenzene, 3',2 dimethyl-4-aminoazobenzene, 2,5-dimethyl-4-aminoazobenzene, 2-methyl-5-methoxy-4-aminoazobenzene, 2-methyl-4',5'-dimethoxy-4-aminoazobenzene, 4'-chloro-2-methyl-5-methoxy-4-aminoazobenzene, 4'-nitro-2-methyl-5-methoxy-4-aminoazobenzene, 4'-chloro-2-methyl-4-aminoazobenzene, 2,5-dimethoxy-4-aminoazobenzene, 4'-chloro-2,5-dimethoxy-4-aminoazobenzene, 4'-nitro-2,5-dimethoxy-4-aminoazobenzene, 4'-chloro-2,5-dimethyl-4-aminobenzene, 4'-methoxy-2,5-dimethyl-4-aminoazobenzene, 4'-nitro-4-aminoazobenzene, 3,5-dibromo-4-aminoazobenzene, 2,3'-dichloro-4-aminoazobenzene, 3-methoxy-4-aminoazobenzene, 1-aminobenzene-2-sulfonic acid, 1-aminobenzene-3-sulfonic acid, 1-aminobenzene-4-sulfonic acid, 1-aminobenzene-2,4-disulfonic acid, 1-aminobenzene-2,5-disulfonic acid, 1-amino-2-methylbenzene-4-sulfonic acid, 1-amino-3-methylbenzene-4-sulfonic acid, 1-amino-4-methylbenzene-2-sulfonic acid, 1-amino-4-methylbenzene-3-sulfonic acid, 2-nitraooaniline-4-sulfonic acid, 4-nitroaniline-2-sulfonic acid, 2-chloroaniline-4-sulfonic acid, 2-chloroaniline-5-sulfonic acid, 3-chloroaniline-6-sulfonic acid, 4-chloroaniline-2-sulfonic acid, 1-amino-3,4-dichlorobenzene- 6-sulfonic acid, 1-amino-2,5-dichlorobenzene-4-sulfonic acid, 1-amino-4-methyl-5-chlorobenzene-2-sulfonic acid, 1-amino-3-methyl-4-chlorobenzene-6-sulfonic acid 2-amino-4-sulfobenzoic acid, 1-amino-4-acetaminobenzene-2-sulfonic acid, 1-amino-5-acetaminobenzene-2-sulfonic acid, 1-amino-2-methoxy-4-nitrobenzene-5-sulfonic acid, 1-aminoanthraquinone-2-sulfonic acid, 1-aminonaphthalene-2-sulfonic acid, 1-aminonaphthalene-4-sulfonic acid, 2-aminonaphthalene-1-sulfonic acid, and the diazo components of the formulae: ##STR34##

Particular industrial significance attaches to dyes of the formula (Ia):

    D.sup.1 --N═N--A.sup.1                                 (Ia)

in which D¹ is: ##STR35##

p is zero or 1;

Y is hydrogen, cyano, chloro, bromo, methylsulfone, ethylsulfone, phenylsulfone, carbalkoxy or SO₃ H;

Y¹ is hydrogen, chloro, bromo or SO₃ H;

Y² is hydrogen, chloro, bromo, methyl, carbalkoxy, 2-benzothiazolyl or SO₃ H;

X is hydrogen, methyl, hydroxy, methoxy or SO₃ H;

X¹ is hydrogen, methyl, methoxy or SO₃ H;

X² is hydrogen, methyl or methoxy;

T is hydrogen or a substituent; and

A¹ has the above meanings.

Preferred radicals T are alkyls of two to eight carbon atoms which may be interrupted by oxygen and may bear hydroxy, phenoxy or OSO₃ H as a substituent, benzyl, benzyl bearing SO₃ H as a substituent, phenylethyl, phenylethyl bearing SO₃ H as a substituent, and phenyl which may bear SO₃ H and/or other radicals as a substituent.

Examples of radicals T are: CH₃, C₂ H₅, C₃ H₇, C₄ H₉, C₆ H₁₃, ##STR36## CH₂ CH₂ OH, (CH₂)₃ OH, CH₂ CH₂ OCH₂ CH₂ OH, (CH₂)₃ O(CH₂)₄ OH, CH₂ CH₂ OC₆ H₅, CH₂ CH₂ OSO₃ H, (CH₂)₃ OSO₃ H, CH₂ CH₂ OCH₂ CH₂ OSO₃ H, (CH₂)₃ O(CH₂)₄ OSO₃ H, CH₂ C₆ H₅, CH₂ C₆ H₄ SO₃ H, C₂ H₄ C₆ H₅, C₂ H₄ C₆ H₄ SO₃ H, C₆ H₅, C₆ H₄ SO₃ H, ##STR37##

Preferred radicals for R and R³ in the radicals A¹ in dyes of the formula (Ia) are alkyl of one to eight carbon atoms which may be interrupted by oxygen and may bear hydroxy, phenoxy, benzoyloxy or OSO₃ H as a substituent, benzyl, phenylethyl or benzyl or phenylethyl bearing SO₃ H as a substituent, unsubstituted or substituted phenyl or hydroxysulfonylphenyl radicals or hydrogen. Preferred also are dyes in which the radical A¹ corresponds to the formula (IVb) and in which R and R¹ together with the nitrogen form the radical of pyrrolidine, piperidine or morpholine.

The SO₃ H groups may be situated preferably either only in the radical D or only in the radical Z, particularly when Z contains a phenyl radical.

Examples of preferred diazo components are: the methyl, ethyl, n-propyl, isopropyl, β-methoxyethyl esters of 2-aminobenzoic, 3-aminobenzoic and 4-aminobenzoic acid, the methyl, ethyl or isopropyl ester of 2-amino-3,5-dichlorobenzoic acid, the methyl, ethyl or β-methoxyethyl ester of 2-amino-3,5-dibromobenzoic acid, ethyl 3-bromo-4-aminobenzoate, diethyl aminoterephthalate, 2-aminobenzonitrile, 2,4-dicyanoaniline, 2-amino-5-chlorobenzonitrile, 2-amino-5-bromobenzonitrile, 2-amino-3-bromo-5-chlorobenzonitrile, 2-amino-3,5-dibromobenzonitrile, 2-amino-3,5-dichlorobenzonitrile, 2-amino-1-trifluoromethylbenzene, 2-amino-5-chlorotrifluoromethylbenzene, 4-aminobenzene-1-methylsulfone, 3-chloro-4-aminobenzene-1-methylsulfone, 2-aminodiphenylsulfone, 4-aminodiphenylsulfone, the β-hydroxyethylimide of 3-aminophthalic or 4-aminophthalic acid, the β-methoxyethylimide of 3-aminophthalic or 4-aminophthalic acid, the butylimide or tolylimide of 3-aminophthalic acid or 4- aminophthalic acid, 1-amino-4-nitrobenzene, 1-amino-4-acetylaminobenzene, 1-amino-3-acetylaminobenzene, 4-aminobenzoic acid amide, the N-methylamide, N-butylamide or N-β-ethylhexylamide of 4-aminobenzoic acid, the N,N-diethylamide of 4-aminobenzoic acid, the amide of 3-aminobenzenesulfonic acid or 4-aminobenzenesulfonic acid, the N-butylamide of 2-aminobenzenesulfonic acid or 4-aminobenzenesulfonic acid, the morpholide of 3-aminobenzenesulfonic acid or 4-aminobenzenesulfonic acid, 2-chloroaniline-4-sulfonic acid, 2-chloroaniline-5-sulfonic acid, 3-chloroaniline-6-sulfonic acid, 4-chloroaniline-2-sulfonic acid, 1-amino-3,4-dichlorobenzene-6-sulfonic acid, 1-amino-2,5-dichlorobenzene-4-sulfonic acid, 1-amino-2,5-dibromobenzene-4- sulfonic acid, 1-amino-4-methyl-5-chlorobenzene-2-sulfonic acid, 1-amino-3-methyl-4-chlorobenzene-6-sulfonic acid and the amines of the formulae: ##STR38## E ═ H, CH₃, C₂ H₅.

The new dyes are yellow to violet, have very high color strength and are suitable for dyeing natural and synthetic polyamides such as wool, silk, nylon 6 or nylon 6,6. Brilliant colorations having excellent fastness properties are obtained with them. Individual fastness properties which should be mentioned are those given in the Color Index for Acid Dyes, in particular light fastness, fastness to rubbing milling, perspiration, potting, water, sea water and washing. The dyes also have very good solubilities, good levelling power and build-up, and the dyeing behavior is essentially independent of the pH.

The following Examples illustrate the invention. References to parts and percentages in the following Examples are by weight unless stated otherwise.

EXAMPLE 1

18 parts of 4-aminoazobenzene-3,4'-disulfonic acid is dissolved in 125 parts by volume of water while hot with an addition of 4 parts of sodium hydroxide. The calculated amount of a 23% sodium nitrite solution is added and then the whole is then added to a mixture of 15 parts by volume of concentrated hydrochloric acid, 100 parts by volume of water and 150 parts of ice. The suspension is stirred for another three hours to complete the diazotization and then added to a solution of 15 parts of 2-phenyl-4,6-bis-γ-hydroxypropylaminopyrimidine in 100 parts by volume of dimethylformamide and 500 parts by volume of ice water. After a pH of 4 to 5 has been set up the mixture is stirred until coupling is completed. The dye of the formula: ##STR39## is then precipitated with common salt, filtered, washed with a dilute solution of common salt and dried. The product dyes polyamide material, for example fibers of poly-ε-caprolactam red hues having very good fastness to light and wet treatment.

EXAMPLE 2

8.3 parts of 4-aminoazobenzene-4'-sulfonic acid is dissolved neutral in 75 parts by volume of water at 70° C., 9 parts by volume of a 23% sodium nitrite solution is added and the solution obtained is then cooled by adding ice to 10° C. The mixture is then acidified with 9 parts by volume of concentrated hydrochloric acid and stirred at ambient temperature until diazotization is over. The suspension is then added to 9.2 parts of 2-piperidino-4-methyl-6-hydroxyethoxyethylaminopyrimidine which has previously been dissolved in 100 parts by volume of formamide, 20 parts by volume of dilute hydrochloric acid and 500 parts by volume of ice-water. Coupling is carried out at a pH of 6.5 to 7. After the reaction is over the pH of the solution is adjusted to 8, the dye which in the form of the free acid corresponds to the formula: ##STR40## is precipitated with sodium chloride and isolated in the usual way. An orange brown powder is obtained which colors polyamide orange hues having good light and wet fastness properties.

EXAMPLE 3

A solution of 12 parts of 2,5-dichlorosulfanilic acid in 120 parts by volume of dilute caustic soda solution (pH 8) is united with the calculated amount of a 23% sodium nitrite solution and added to 9 parts by volume of concentrated hydrochloric acid and 100 parts of ice. Diazotization is over within two hours at 0° to 5° C. The suspension obtained is added to a mixture of 8.6 parts of 2-phenyl-4-β-hydroxyethylamino-6-β-methoxyethylaminopyrimidine (previously dissolved in dilute hydrochloric acid) and 200 parts of ice and the whole is adjusted with 10% caustic soda solution to a pH of 6 to 7 and stirred overnight. The deposited dye is brought into solution by heating at pH 10, the dye salt is precipitated with sodium chloride, filtered off and dried. The dye in the form of the free acid corresponds to the formula: ##STR41## it dyes polyamide materials yellow hues of outstanding light and wet fastness properties.

EXAMPLE 4

9 parts of the coupling product of sulfanilic acid and 2,5-dimethylaniline is diazotized in the usual way in 200 parts by volume of water in the presence of 10 parts by volume of concentrated hydrochloric acid with sodium nitrite at ambient temperature. The diazotization mixture is then coupled with a solution of 8.6 parts of 2-phenyl-4-β-hydroxyethylamino-6-β-methoxyethylaminopyrimidine in 100 parts by volume of formamide and 250 parts of ice, the pH being adjusted to 5.5 and the mixture stirred until coupling is over. The deposited dye is then filtered off, dissolved in dilute caustic soda solution, again precipitated with sodium chloride, filtered off and dried. The compound corresponds in the form of the free acid to the formula: ##STR42## It dyes polyamide materials yellowish red hues of outstanding fastness properties.

The following dyes are also prepared by methods analogous to those described in the foregoing Examples.

    __________________________________________________________________________      ##STR43##                                                                                                                               Hue of                                                                         dyeing               Ex.                                                       on poly-             No.                                                                               DK               X.sup.1     X.sup.2     X.sup.3       amide                __________________________________________________________________________      5                                                                                 ##STR44##                                                                                       ##STR45##  NHC.sub.2 H.sub.4 OCH.sub.3                                                                NHC.sub.2 H.sub.4 OCH.sub.3                                                                  yellow                6 "                "           NHC.sub.2 H.sub.4 OH                                                                       NHC.sub.2 H.sub.4 OH                                                                         yellow                7 "                                                                                                ##STR46##  CH.sub.3    NH(CH.sub.2).sub.3 OCH.sub.3                                                                 yellow                8 "                "           "           NHC.sub.2 H.sub.4 OH                                                                         yellow                9                                                                                 ##STR47##       "           "           "             yellow               10 "                "           "           NH(CH.sub.2).sub.3 OCH.sub.3                                                                 yellow               11 "                                                                                                ##STR48##  NHC.sub.2 H.sub.4 OCH.sub.3                                                                NHC.sub.2 H.sub.4 OCH.sub.3                                                                  yellow               12 "                "           NHC.sub.2 H.sub.4 OH                                                                       NHC.sub.2 H.sub.4 OH                                                                         yellow               13                                                                                 ##STR49##       "           "           "             yellow               14 "                "           NHC.sub.2 H.sub.4 OCH.sub.3                                                                NHC.sub.2 H.sub.4l                                                                           yellowb.3            15 "                                                                                                ##STR50##  CH.sub.3    NH(CH.sub.2).sub.3 OCH.sub.3                                                                 yellow               16 "                "           "           NHC.sub.2 H.sub.4 OH                                                                         yellow               17                                                                                 ##STR51##       "           "           "             yellow               18 "                "           "           NH(CH.sub.2).sub.3 OCH.sub.3                                                                 yellow               19 "                                                                                                ##STR52##  NHC.sub.2 H.sub.4 OCH.sub.3                                                                NHC.sub.2 H.sub.4 OCH.sub.3                                                                  yellow               20 "                "           NHC.sub.2 H.sub.4 OH                                                                       NHC.sub.2 H.sub.4 OH                                                                         yellow               21                                                                                 ##STR53##       "           "           "             yellow               22 "                "           NHC.sub.2 H.sub.4 OCH.sub.3                                                                NHC.sub.2 H.sub.4 OCH.sub.3                                                                  yellow               23                                                                                 ##STR54##       "           "           NHC.sub.2 H.sub.4 OH                                                                         yellow               24 "                                                                                                ##STR55##  CH.sub.3    NH(C.sub.2 H.sub.4 O).sub.2                                                                  yellow               25                                                                                 ##STR56##                                                                                       ##STR57##  NHC.sub.2 H.sub.4 OH                                                                       NHC.sub.2 H.sub.4 OH                                                                         yellow               26 "                "           NH(CH.sub.2).sub.3 OH                                                                      NH(CH.sub.2).sub.3 OH                                                                        yellow               27 "                "           NHC.sub.2 H.sub.4 OCH.sub.3                                                                NHC.sub.2 H.sub.4 OCH.sub.3                                                                  yellow               28 "                ∝    NH(CH.sub.2).sub.3 OCH.sub.3                                                               NH(CH.sub.2).sub.3 OCH.sub.3                                                                 yellow               29 "                "           NHC.sub.2 H.sub.4 OH                                                                       NHC.sub.2 H.sub.5                                                                            yellow               30 "                "           "           NHC.sub. 4 H.sub.9                                                                           yellow               31 "                "           "           NH.sub.2      yellow               32 "                "           "                                                                                           ##STR58##    yellow               33 "                "           NH.sub.2    "             yellow               34 "                "           NHC.sub.2 H.sub.4 OH                                                                       NH(CH.sub.2).sub.3 OCH.sub.3                                                                 yellow               35 "                "           "           NH(CH.sub.2).sub.3 OC.sub.3                                                    H.sub.7 (i)   yellow               36 "                "           NH.sub.2    NH(CH.sub.2).sub.3 O(CH.sub.2)                                                 .sub.4 OH     yellow               37 "                "           NHC.sub.2 H.sub.4 OH                                                                        ##STR59##    yellow               38 "                "           "                                                                                           ##STR60##    yellow               39 "                "           "           NH(CH.sub.2).sub.3 OCH.sub.2                                                   C.sub.6 H.sub.5                                                                              yellow               40 "                "           "           NHCH.sub.2 C.sub.6 H.sub.5                                                                   yellow               41 "                "           NH(CH.sub.2).sub.3 OH                                                                      "             yellow               42 "                "           NHC.sub.2 H.sub.4 OH                                                                        ##STR61##    yellow               43 "                "           "           NHC.sub.6 H.sub.5                                                                            yellow               44 "                "           NH(C.sub.2 H.sub.4 O).sub.2 H                                                              "             yellow               45 "                                                                                                ##STR62##  NHC.sub.2 H.sub.4 OH                                                                       MHC.sub.2 H.sub.4 OH                                                                         yellow               46 "                "                                                                                           ##STR63##  NH(CH.sub.2).sub.3 OC.sub.3                                                    H.sub.7 (i)   yellow               47 "                                                                                                ##STR64##                                                                                  ##STR65##  NH)h.sub.2).sub.3 OCH.sub.3                                                                  yellow               48 "                                                                                                ##STR66##  NHC.sub.2 H.sub.4 OH                                                                       NH(CH.sub.2).sub.3 OC.sub.3                                                    H.sub.7 (i)                        49 "                                                                                                ##STR67##  NH(C.sub.2 H.sub.4 O).sub.2 H                                                              NH(C.sub.2 H.sub.4 O).sub.2                                                                  yellow               50 "                H           NH(CH.sub.2).sub.3 OH                                                                      NH(CH.sub.2).sub.3 OCH.sub.3                                                                 yellow               51 "                CH.sub.3    NHC.sub.2 H.sub.4 OCH.sub.3                                                                NHC.sub.2 H.sub.4 OCH.sub.3                                                                  yellow               52 "                "           NH(CH.sub.2).sub.3 OH                                                                       ##STR68##    yellow               53 "                CH(CH.sub.3).sub.2                                                                         NH(CH.sub.2).sub.3 OCH.sub.3                                                               NH(CH.sub.2).sub.3 OCH.sub.3                                                                 yellow               54 "                C.sub.4 H.sub.9                                                                            NH(CH.sub.2).sub.3 OH                                                                      NH(CH.sub.2).sub.3 OH                                                                        yellow               55 "                                                                                                ##STR69##  "           "             yellow               56 "                                                                                                ##STR70##  "           "             yellow               57 "                CH.sub.2 OCH.sub.2 H.sub.5                                                                 "           "             yellow               58 "                                                                                                ##STR71##  "           "             yellow               59 "                N(C.sub.2 H.sub.5).sub.2                                                                   H           NHC.sub.6 H.sub.5                                                                            yellow               60 "                                                                                                ##STR72##  CH.sub.3    NHC.sub.2 H.sub.4 OH                                                                         yellow               61 "                "           "           NH(C.sub.2 H.sub.4 O).sub.2                                                                  yellow               62 "                "           "           NH(CH.sub.2).sub.3 OH                                                                        yellow               63 "                "           "           NH(CH.sub.2                                                                                  yellow3 OCH.sub.     64 "                "           "           NHCH.sub.2 C.sub.6 H.sub.5                                                                   yellow               65 "                N(C.sub.2 H.sub.5).sub.2                                                                   "           NHC.sub.2 H.sub.4 C.sub.6                                                      H.sub.5       yellow               66                                                                                 ##STR73##                                                                                       ##STR74##  NHC.sub.2 H.sub.4 OH                                                                       NHC.sub.2 H.sub.4 OH                                                                         yellowish                                                                      orange               67                                                                                 ##STR75##       "           "           "             yellow               68                                                                                 ##STR76##       "           "           "             yellow               69                                                                                 ##STR77##       "           "           "             yellow               70                                                                                 ##STR78##       "           "           NHC.sub.4 H.sub.9                                                                            orange               71 "                                                                                                ##STR79##  CH.sub.3    NHC.sub.2 H.sub.4 OH                                                                         yellow               72                                                                                 ##STR80##                                                                                       ##STR81##  NHC.sub.2 H.sub.4 OH                                                                       NHC.sub.2 H.sub.4 OH                                                                         reddish orange       73 "                "           NH(CH.sub.2).sub.3 OH                                                                      NH(CH.sub.2).sub.3 OH                                                                        "                    74 "                "           NH(CH.sub.2).sub.3 OCH.sub.3                                                               NH(CH.sub.2).sub.3 OCH.sub.3                                                                 "                    75 "                "           NHC.sub.2 H.sub.4 OCH.sub.3                                                                NHC.sub.2 H.sub.4 OCH.sub.3                                                                  "                    76 "                "           NHC.sub.2 H.sub.4 OH                                                                       NHC.sub.4 H.sub.9                                                                            "                    77 "                                                                                                ##STR82##  NH(CH.sub.2).sub.3 OH                                                                      NH(CH.sub.2).sub.3 OCH.sub.3                                                                 "                    78 "                                                                                                ##STR83##  NH(CH.sub.2).sub.3 OCH.sub.3                                                               "             orange               79 "                                                                                                ##STR84##  CH.sub.3    NHC.sub.2 H.sub.4 OH                                                                         orange               80 "                "           "           NH(CH.sub.2).sub.3 OCH.sub.3                                                                 "                    81                                                                                 ##STR85##                                                                                       ##STR86##  NHC.sub.2 H.sub.4 Oh                                                                       NHC.sub.2 H.sub.4 OH                                                                         yellowish red        82 "                "           NH(CH.sub.2).sub.3 OH                                                                      NH(CH.sub.2).sub.3 OH                                                                        "                    83 "                "           NHC.sub.2 H.sub.4 OCH.sub.3                                                                NHC.sub.2 H.sub.4 OCH.sub.3                                                                  "                    84 "                "           NH(CH.sub.2).sub.3 OCH.sub.3                                                               NH(CH.sub.2).sub.3 OCH.sub.3                                                                 "                    85 "                "                                                                                           ##STR87##  "             "                    86 "                "           NH.sub.2    NH.sub.2      orange               87 "                "           NH(CH.sub.2).sub.6 OH                                                                      NHC.sub.2 H.sub.4 OCH.sub.3                                                                  yellowish red        88 "                "           NH(CH.sub.2).sub.3 OC.sub.2 H.sub.4                                                        "H            "                    89 "                "           NH(CH.sub.2).sub.3 O(CH.sub.2).sub.6                                                       "H            "                    90 "                "           NHC.sub.2 H.sub.4 OH                                                                       NH(CH.sub.2).sub.3 OCH.sub.2                                                   C.sub.6 H.sub.5                                                                              yellowish red        91 "                                                                                                ##STR88##  "           NHC.sub.4 H.sub.9                                                                            "                    92 "                                                                                                ##STR89##  NH(CH.sub.2).sub.3 OCH.sub.3                                                               NH(CH.sub.2).sub.3 OCH.sub.3                                                                 "                    94 "                                                                                                ##STR90##  CH.sub.3    NH(C.sub.2 H.sub.4 O).sub.2                                                    COCH.sub.3    orange               95 "                                                                                                ##STR91##  "           "             "                    96 "                N(C.sub.3 H.sub.7).sub.2                                                                   "           "             "                    97                                                                                 ##STR92##                                                                                       ##STR93##  NH.sub.2    NH.sub.2      "                    98 "                "           NHC.sub.2 H.sub.4 OH                                                                       NHC.sub.2 H.sub.4 OH                                                                         red                  99 "                "           NH(C.sub.2 H.sub.4 O).sub.2 H                                                              NH(C.sub.2 H.sub.4 O).sub.2                                                                  "                    100                                                                               "                "           NHC.sub.2 H.sub.4 OCH.sub.3                                                                "                                  101                                                                               "                "           NH(CH.sub.2).sub.3 OCH.sub.3                                                               NH(CH.sub.2).sub.3 OCH.sub.3                                                                 "                    102                                                                               "                "           NH.sub.2                                                                                    ##STR94##    red                  103                                                                               "                "           NHC.sub.2 H.sub.4 OH                                                                       NHC.sub.2 H.sub.5                                                                            "                    104                                                                               "                "           "           NHC.sub.3 H.sub.7                  105                                                                               "                "           "           NHC.sub.3 H.sub.7                                                                            "                    105                                                                               "                "           "           NHC.sub.6 H.sub.13                                                                           "                    106                                                                               "                "           NH(CH.sub.2).sub.3 OH                                                                      NH(CH.sub.2).sub.3 OC.sub.2                                                    H.sub.4 OC.sub.2 H.sub.5                                                                     "                    107                                                                               "                "           "           NH(CH.sub.2).sub.3 OC.sub.2                                                    H.sub.4 OC.sub.6 H.sub.5                                                                     "                    108                                                                               "                "           "           NH(CH.sub.2).sub.3 OC.sub.2                                                    H.sub.5       "                    109                                                                               "                "           "           NH(CH.sub.2).sub.3 OC.sub.2                                                    H.sub.4 C.sub.6 H.sub.5                                                                      "                    110                                                                               "                "           "                                                                                           ##STR95##    "                    111                                                                               "                "           "                                                                                           ##STR96##    "                    112                                                                               "                "           "                                                                                           ##STR97##    "                    113                                                                               "                "           NH(CH.sub.2).sub.3 O(CH.sub.2).sub.4                                                       NHC.sub.2 H.sub.4 OCH.sub.3                                                                  red                  114                                                                               "                "           NHC.sub.2 H.sub.4 OH                                                                       NHCH.sub.2 C.sub.6 H.sub.5                                                                   "                    115                                                                               "                "           "           NHC.sub.2 H.sub.4 C.sub.6                                                      H.sub.5       "                    116                                                                               "                "           "           NHC.sub.6 H.sub.5                                                                            "                    117                                                                               "                "           NH(CH.sub.2).sub.3 OH                                                                       ##STR98##    "                    118                                                                               "                                                                                                ##STR99##  NHC.sub.2 H.sub.4 OH                                                                       NHC.sub.4 H.sub.9                                                                            "                    119                                                                               "                                                                                                ##STR100## NH(CH.sub.2).sub.3 OCH.sub.3                                                               NH(CH.sub.2).sub.3 OCH.sub.3                                                                 "                    120                                                                               "                                                                                                ##STR101## NH(CH.sub.2).sub.3 OH                                                                      NH(CH.sub.2).sub.3 OH                                                                        "                    121                                                                               "                N(C.sub.2 H.sub.5).sub.2                                                                   H           NHC.sub.2 H.sub.4 OH                                                                         orange               122                                                                               "                "           "           NHC.sub.6 H.sub.5                                                                            "                    123                                                                               "                N(CH.sub.3).sub.2                                                                          CH.sub.3    NH(CH.sub.2).sub.3 OH                                                                        yellowish                                                                      red                  124                                                                               "                N(C.sub.2 H.sub.5).sub.2                                                                   "           NH(CH.sub.2).sub.3 O(CH.sub.2)                                                 .sub.4 OH     yellowish                                                                      red                  125                                                                               "                "           "                                                                                           ##STR102##   "                    126                                                                               "                "           "           NH(CH.sub.2).sub.3 OCH.sub.2                                                   C.sub.6 H.sub.5                                                                              "                    127                                                                               "                "           "                                                                                           ##STR103##   "                    128                                                                               "                "           "                                                                                           ##STR104##   "                    129                                                                               "                "           "           NHCH.sub.2 C.sub.6 H.sub.5                                                                   "                    130                                                                               "                "           "                                                                                           ##STR105##   "                    131                                                                               "                "           "                                                                                           ##STR106##   "                    132                                                                               "                N(C.sub.3 H.sub.7).sub.2                                                                   "           NH(CH.sub.2).sub.3 OH                                                                        "                    133                                                                               "                "           "           NHC.sub.2 H.sub.4 C.sub.6                                                      H.sub.5       "                    134                                                                               "                                                                                                ##STR107## "           NH(CH.sub.2).sub.3 OH                                                                        "                    135                                                                               "                                                                                                ##STR108## "           "             yellowish red        136                                                                               "                                                                                                ##STR109## "           "             "                    137                                                                               "                                                                                                ##STR110## "           NH(C.sub.2 H.sub.4 O).sub.2                                                                  "                    138                                                                               "                "           "           NH(CH.sub.2).sub.3 O(CH.sub.2)                                                 .sub.4 OH     "                    139                                                                               "                "           "           NHCH.sub.2 C.sub.6 H.sub.5                                                                   "                    140                                                                               "                "           C.sub.3 H.sub.7                                                                            NH(CH.sub.2).sub.3 OH                                                                        "                    141                                                                               "                "                                                                                           ##STR111## "             "                    142                                                                               "                                                                                                ##STR112## CH.sub.3    "             "                    143                                                                               "                                                                                                ##STR113## "           "             "                    144                                                                                ##STR114##                                                                                      ##STR115## NHC.sub.2 H.sub.4 OH                                                                       NHC.sub.2 H.sub.4 OH                                                                         red                  145                                                                               "                "           NH(CH.sub.2).sub.3 OH                                                                      NH(CH.sub.2).sub.3 OH                                                                        "                    146                                                                               "                "           NH(C.sub.2 H.sub.4 O).sub.2 H                                                              NH(C.sub.2 H.sub.4 O).sub.2                                                                  "                    147                                                                               "                "           NHC.sub.2 H.sub.4 OCH.sub.3                                                                NHC.sub.2 H.sub.4 OCH.sub.3                                                                  "                    148                                                                               "                "           NH(CH.sub.2).sub.3 OCH.sub.3                                                               NH(CH.sub.2).sub.3 OCH.sub.3                                                                 "                    149                                                                               "                                                                                                ##STR116## CH.sub.3    NHC.sub.2 H.sub.4 OH                                                                         yellowish red        150                                                                                ##STR117##                                                                                      ##STR118## NHC.sub.2 H.sub.4 OCH.sub.3                                                                NH(CH.sub.2).sub.3 O(CH.sub.2)                                                 .sub.4 OH     Bordeaux             151                                                                               "                                                                                                ##STR119## CH.sub.3    NHC.sub.2 H.sub.4 OH                                                                         red                  152                                                                                ##STR120##      "           "           "             Bordeaux             153                                                                               "                                                                                                ##STR121## NHC.sub.2 H.sub.4 OH                                                                       NHC.sub.2 H.sub.4 OCH.sub.3                                                                  violet               154                                                                               "                "           NHC.sub.2 H.sub.4 OCH.sub.3                                                                NH(CH.sub.2).sub.3 O(CH.sub.2)                                                 .sub.4 OH     "                    155                                                                                ##STR122##      "           "           "             yellowish red        156                                                                               "                                                                                                ##STR123## CH.sub.3    NHC.sub.2 H.sub.4 OH                                                                         reddish orange       157                                                                                ##STR124##      "           "           "             red                  158                                                                               "                                                                                                ##STR125## NHC.sub.2 H.sub.4 OH                                                                       NHC.sub.2 H.sub.4 OCH.sub.3                                                                  "                    159                                                                                ##STR126##      "           NHC.sub.2 H.sub.4 OCH.sub.3                                                                NH(CH.sub.2).sub.3 O(CH.sub.2)                                                 .sub.4 OH     violet               160                                                                               "                                                                                                ##STR127## CH.sub.3    NHC.sub.2 H.sub.4 OH                                                                         Bordeaux             161                                                                                ##STR128##                                                                                      ##STR129## NHC.sub.2 H.sub.4 OH                                                                       NHC.sub.2 H.sub.4 OCH.sub.3                                                                  yellowish red        162                                                                                ##STR130##      "           "           "             red                  163                                                                               "                                                                                                ##STR131## CH.sub.3    NH(CH.sub.2).sub.3 OH                                                                        yellowish red        164                                                                                ##STR132##      "           "           "             "                    165                                                                               "                                                                                                ##STR133## NHC.sub.2 H.sub.4 OH                                                                       NHC.sub.2 H.sub.4 OCH.sub.3                                                                  red                  166                                                                                ##STR134##      "           "           "             "                    167                                                                               "                                                                                                ##STR135## CH.sub.3    NH(CH.sub.2).sub.3                                                                           yellowish red        168                                                                                ##STR136##      "           "           "             orange               169                                                                               "                                                                                                ##STR137## NHC.sub.2 H.sub.4 OH                                                                       NHC.sub.2 H.sub.4 OCH.sub.3                                                                  red                  170                                                                                ##STR138##      "           "           "             "                    171                                                                                ##STR139##      "           "           NHC.sub.2 H.sub.4 OH                                                                         Bordeaux             172                                                                                ##STR140##      "           "           "             "                    173                                                                                ##STR141##      "           "           "             red                  174                                                                                ##STR142##      "           "           "             violet               175                                                                                ##STR143##      "           "           "             red                  __________________________________________________________________________

EXAMPLE 176

12.7 parts of 2-pyrrolidino-4-phenylamino-6-methyl-pyrimidine is introduced into 63 parts of oleum (23%) while cooling and the mixture is stirred for two hours at ambient temperature. The solution is then poured into ice-water. The sulfonation product having the probable formula. ##STR144## is thus precipitated. It is filtered off, washed with water and dried. The yield is 14.5 parts and the melting point of the compound is above 350° C.

3.5 parts of o-aminobenzonitrile is dissolved in 100 parts by volume of water and 10 parts by volume of concentrated hydrochloric acid. 100 parts of ice is added and diazotization is carried out in the usual way with sodium nitrite. The diazonium salt solution obtained is clarified and added at 0° to 5° C. to a solution of 11 parts of the pyrimidine (obtained by the above method) in 100 parts by volume of water, 10 parts of a 10% caustic soda solution and 200 parts of ice. The pH of the mixture is then adjusted to 6 to 7. After coupling is over the dye whose composition corresponds to the probable formula: ##STR145## is brought into solution by adding caustic soda solution, precipitated with sodium chloride, filtered off and dried. An orange powder is obtained which colors polyamide cloth yellow hues having very good fastness properties.

EXAMPLE 177

15.8 parts of 2-p-tolyl-4,6-bis-β-methoxyethylaminopyrimidine is introduced with slight cooling into 79 parts of oleum (23%) and the mixture is stirred at 35° C. until sulfonation is completed according to a chromatogram. The mixture is then poured into ice-water, the solution is adjusted to pH 7.2 with potassium hydroxide and the potassium salt of the sulfonic acid of the formula: ##STR146## is precipitated with potassium chloride. The product is filtered off, washed with a small amount of water and dried.

12 parts of the compound thus obtained is dissolved in 100 parts by volume of water and 10 parts by volume of a 10% caustic soda solution, then 200 parts of ice is added and coupling is carried out with a solution of the diazonium salt of 3.5 parts of o-aminobenzonitrile. Coupling is over at pH 6 to 7 within a short time. The dye is brought into solution by adding caustic soda solution and the sodium salt is then precipitated with sodium chloride. After isolation in the usual way the dye which in the form of the free acid corresponds to the formula: ##STR147## is obtained as a yellowish brown powder. It dyes polycaprolactam cloth fast yellow hues.

EXAMPLE 178

17 parts of 2-dibutylamino-4-methyl-6-phenylethylaminopyrimidine is introduced into 85 parts of oleum (23%) and heated for three hours at 60° C. The solution is then poured into ice-water. The supernatant aqueous phase is decanted off from the deposited product of the formula: ##STR148## and the compound is dissolved in dilute caustic soda solution.

An aliquot portion of this mixture is coupled with the solution of the diazonium salt of 3.5 parts of o-aminobenzonitrile. The pH is brought to 6 to 7 and the reaction mixture is stirred until coupling has been completed. The precipitated dye of the formula: ##STR149## is then brought into solution with caustic soda solution and precipitated again with sodium chloride. After having been filtered off and dried an orange powder is obtained which colors polycaprolactam material yellow hues which are fast to light and wet.

EXAMPLE 179

24.8 parts of the coupling product from p-aminoazobenzene and 2-phenyl-4-β-hydroxyethylamino-6-β-methoxyethylaminopyrimidine is dissolved in 165 parts of oleum (23%) and the mixture is stirred for three hours at ambient temperature. The solution is then poured into water, the mixture is heated for ninety minutes at 75° C. and the sulfonation product is filtered off and dissolved in dilute caustic soda solution. The solution is filtered and sodium chloride is added to it.

The dye is thus precipitated. In the form of the free acid it has the formula: ##STR150## It is filtered off, washed with a small amount of water and dried. The brown powder obtained dyes polyamide cloth orange hues.

The methods described in Examples 1 to 4 and in Examples 176 to 179 may also be used for the production of the dyes set out in the following Table:

                                                                                      Ex.      No. DK X.sup.1 X.sup.2 X.sup.3 Hue                                            180                                                                      ##STR151##                                                                      ##STR152##                                                                      NHC.sub.2 H.sub.5 NHC.sub.2                                                     H.sub.5 yellow 181                                                             ##STR153##                                                                       " " " " 182 " N(C.sub.2 H.sub.5).sub.2 CH.sub.3 NHC.sub.6 H.sub.4              SO.sub.3                                                                         H " 183                                                                        ##STR154##                                                                       ##STR155##                                                                      NHC.sub.2 H.sub.4 OH NHC.sub.2 H.sub.4                                          OCH.sub.3 orange 184                                                           ##STR156##                                                                       " " " " 185                                                                     ##STR157##                                                                      " " " reddish yellow 186 "                                                      ##STR158##                                                                      CH.sub.3 NHC.sub.2 H.sub.4 C.sub.6 H.sub.4 SO.sub.3 H yellow 187                ##STR159##                                                                      ##STR160##                                                                      NH.sub.2 NH.sub.2 " 188 " " " NHC.sub.2 H.sub.4                                 OH " 189 " " " NH(CH.sub.2).sub.3 OCH.sub.3 " 190 " " NHC.sub.2 H.sub.4        OH NHC.sub.2 H.sub.5 reddish      yellow 191 " " " NH(CH.sub.2).sub.3           OCH.sub.3 " 192 " " " NHC.sub.6 H.sub.5 orange 193 " N(C.sub.2                   H.sub.5).sub.2 H NHC.sub.2 H.sub.4 C.sub.6 H.sub.4 SO.sub.3 H yellow           194 " " CH.sub.3 NHCH.sub.2 C.sub.6 H.sub.4 SO.sub.3                             H "  195 "                                                                     ##STR161##                                                                       " NHC.sub.2 H.sub.4 OCH.sub.3 " 196 " N(C.sub.2 H.sub.5).sub.2 "               NH(CH.sub.2).sub.3 OCH.sub.2 C.sub.6 H.sub.4 SO.sub.3                            H " 197                                                                        ##STR162##                                                                       ##STR163##                                                                      NHC.sub.2 H.sub.4 OH NH(CH.sub.2).sub.3 OCH.sub.3 reddishyellow 198             ##STR164##                                                                      " " " " 199                                                                     ##STR165##                                                                      " " NHC.sub.2 H.sub.4 OH orange 200 " " NH(C.sub.2 H.sub.4 O).sub.2 H          NH(C.sub.2 H.sub.4 O).sub.2                                                      H " 201                                                                        ##STR166##                                                                       " NHC.sub.2 H.sub.5 NHC.sub.2 H.sub.5 " 202 " " NHC.sub.2 H.sub.4 OH           NHC.sub.6 H.sub.5 " 203 " N(C.sub.2                                              H.sub.5).sub.2 CH.sub.3 NH(CH.sub.2).sub.3 OCH.sub.3 reddish                   yellow 204 " " " NHCH.sub.2 C.sub.6                                              H.sub.5 " 205 "                                                                ##STR167##                                                                       " NH(CH.sub.2).sub.3 O(CH.sub.2).sub.4                                          OH " 206                                                                       ##STR168##                                                                       ##STR169##                                                                      NHC.sub.2 H.sub.4 OH NHC.sub.2 H.sub.4                                          OH " 207                                                                       ##STR170##                                                                       ##STR171##                                                                      " NHCH.sub.2 C.sub.6 H.sub.4 SO.sub.3                                           H yellow 208 "                                                                 ##STR172##                                                                       NH.sub.2 NH.sub.2 " 209 " " NH.sub.2 NH(CH.sub.3).sub.2                         O(CH.sub.2).sub.4 OH " 210 " " NHC.sub.2 H.sub.4 OH NHC.sub.2 H.sub.5 "        211 " " " NH(CH.sub.2).sub.3 OCH.sub.3 " 212 " " " NHC.sub.6 H.sub.4            SO.sub.3 H " 213 " " NH(CH.sub.2).sub.3 OH " " 214 " " NHC.sub.2 H.sub.4        OH NHC.sub.6 H.sub.5 " 215 " " " NH(CH.sub.2).sub.3 OC.sub.2 H.sub.4            C.sub.6 H.sub.5 " 216 " " " NH(CH.sub.2).sub.3 OC.sub.2 H.sub.4                  OCH.sub.3 " 217 " " NHC.sub.2 H.sub.4 OCOCH.sub.3 " " 218 " " NHC.sub.2        H.sub.4                                                                          OH                                                                             ##STR173##                                                                       " 219 " " "                                                                     ##STR174##                                                                      " 220 " " NHC.sub.2 H.sub.5 NHC.sub.6 H.sub.3 (OCH.sub.3)SO.sub.3 H "          221 "                                                                            ##STR175##                                                                      NH(CH.sub.2).sub.3 OH NH(CH.sub.2).sub.3 OC.sub.3 H.sub.7 (i) " 222 "           ##STR176##                                                                      " NH(CH.sub.2).sub.3                                                            OCH.sub.3 " 223 "                                                              ##STR177##                                                                       NH(C.sub.2 H.sub.4 O).sub.2 H NH(C.sub.2 H.sub.4 O).sub.2 H " 224 "            CH.sub.3 NHC.sub.6 H.sub.4 SO.sub.3 H NHC.sub.2 H.sub.4 OCH.sub.3 " 225         " CH(CH.sub.3).sub.2 NHC.sub.2 H.sub.4 C.sub.6 H.sub.4 SO.sub.3 H " "           226 "                                                                            ##STR178##                                                                      NH(CH.sub.2).sub.3 OH NH(CH.sub.2).sub.3 OH " 227 " N(C.sub.2                   H.sub.5).sub.2 H NHC.sub.6 H.sub.4 SO.sub.3 H " 228 " " CH.sub.3               NHC.sub.2 H.sub.4 C.sub.6 H.sub.4 SO.sub.3                                       H " 229 "                                                                      ##STR179##                                                                       " NHCH.sub.2 C.sub.6 H.sub.4 SO.sub.3                                           H " 230                                                                        ##STR180##                                                                       " " " " 231 " N(C.sub.2 H.sub.5).sub.2 " NHC.sub.2 H.sub.4 C.sub.6             H.sub.4 SO.sub.3                                                                 H " 232 "                                                                      ##STR181##                                                                       NHC.sub.2 H.sub.4 OH NH(CH.sub.2).sub.3 OCH.sub.3 " 233 " " " NHC.sub.6        H.sub.5 " 234 " " NH(CH.sub.2).sub.3 OH NHC.sub.6 H.sub.4 SO.sub.3 H "          235 " " NHC.sub.2 H.sub.4 OH NHC.sub. 2 H.sub.4 OH " 236 " " NHC.sub.2          H.sub.4 OCOCH.sub.3 NHC.sub.2 H.sub.4                                            OCOCH.sub.3 " 237 " "                                                          ##STR182##                                                                       ##STR183##                                                                      " 238 " " NHC.sub.2 H.sub.4 OCOCH.sub.2 COCH.sub.3 NHC.sub.2 H.sub.4           OCOCH.sub.2                                                                      COCH.sub.3 " 239                                                               ##STR184##                                                                       " NHC.sub.2 H.sub.4 OH NHC.sub.2 H.sub.4                                        OH orange 240                                                                  ##STR185##                                                                       ##STR186##                                                                      " NHC.sub.6 H.sub.4 SO.sub.3                                                    H " 241                                                                        ##STR187##                                                                       " " " yellow 242                                                                ##STR188##                                                                      ##STR189##                                                                      NHC.sub.2 H.sub.5 NHC.sub. 2 H.sub.5 orange 243 " " NH(C.sub.2 H.sub.4         O).sub.2 H NHC.sub.2 H.sub.4                                                     OCH.sub.3 " 244 "                                                              ##STR190##                                                                       CH.sub.3 NHCH.sub.2 C.sub.6 H.sub.4 SO.sub.3                                    H " 245                                                                        ##STR191##                                                                       ##STR192##                                                                      NHC.sub.2 H.sub.4 OH NHC.sub.2 H.sub.4 OH reddishyellow 246 " "                NHC.sub.2 H.sub.4 OH NHCH.sub.2 C.sub.6 H.sub.4 SO.sub.3 H " 247 "              N(C.sub.2 H.sub.5).sub.2 CH.sub.3 NHC.sub.2 H.sub.4 C.sub.6 H.sub.4             SO.sub.3 H yellow 248 " CH.sub.3 NHC.sub.2 H.sub.4 C.sub.6 H.sub.4              SO.sub.3 H NHC.sub.2 H.sub.4                                                     OCH.sub.3 " 249                                                                ##STR193##                                                                       ##STR194##                                                                      NHC.sub.2 H.sub.4 OH NHC.sub.2 H.sub.4                                          OH reddishyellow 250                                                           ##STR195##                                                                       " NHC.sub.2 H.sub.5 NHC.sub.2                                                   H.sub.5 yellow 251 "                                                           ##STR196##                                                                       NHC.sub.2 H.sub.4 OH NHC.sub.2 H.sub.4                                          OH " 252                                                                       ##STR197##                                                                       ##STR198##                                                                      NHC.sub.2 H.sub.4 OH NH(CH.sub.2).sub.3 OCH.sub.2 C.sub.6 H.sub.4              SO.sub.3 H " 253 " N(C.sub.2 H.sub.5).sub.2 CH.sub.3 NHC.sub.2 H.sub.4          C.sub.6 H.sub.4 SO.sub.3 H " 254 " CH.sub.3 NHC.sub.2 H.sub.4 OCH.sub.3         " " 255                                                                          ##STR199##                                                                      ##STR200##                                                                      NHC.sub.2 H.sub.4 OH NH(CH.sub.2).sub.3 OCH.sub.2 C.sub.6 H.sub.4              SO.sub.3                                                                         H " 256                                                                        ##STR201##                                                                       " " NHC.sub.2                                                                   H.sub.4 OCH.sub.3 orange 257                                                   ##STR202##                                                                       " " " yellow 258 " N(C.sub.2 H.sub.5).sub.2 CH.sub.3 NHC.sub.2 H.sub.4         C.sub.6 H.sub.4 SO.sub.3                                                         H " 259                                                                        ##STR203##                                                                       ##STR204##                                                                      NHC.sub.2 H.sub.4 OH NHC.sub.2 H.sub.4 OH " 260 " " " NHCH.sub.2               C.sub.6 H.sub.4 SO.sub.3                                                         H " 261                                                                        ##STR205##                                                                       " " NHC.sub.2 H.sub.4                                                           OH " 262                                                                       ##STR206##                                                                       " " " " 263                                                                     ##STR207##                                                                      " " " " 264 "                                                                   ##STR208##                                                                      CH.sub.3 NHCH.sub.2 C.sub.6 H.sub.4 SO.sub.3                                    H " 265                                                                        ##STR209##                                                                       ##STR210##                                                                      NHC.sub.2 H.sub.4 OH NHC.sub.2 H.sub.4 OH " 266 " " NHC.sub.2 H.sub.4          OCOCH.sub.3 NHC.sub.2 H.sub.4 OCOCH.sub.3 " 267 " " NHC.sub.2 H.sub.4 OH        NH(CH.sub.2).sub.3 OC.sub.2 H.sub.4 OC.sub.6                                     H.sub.5 " 268 " " NH(CH.sub.2).sub.3 OH NHC.sub.6 H.sub.4 SO.sub.3 H "         269                                                                              ##STR211##                                                                      " NH.sub.2 NHC.sub.2 H.sub.4 OH orange 270 " " NHC.sub.2 H.sub.4 OH            NH(CH.sub.2).sub.3                                                               OCH.sub.3 reddish      orange 271 " " " NH(CH.sub.2).sub.3 OCH.sub.2           C.sub.6 H.sub.4 SO.sub.3 H " 272 " " " NHC.sub.2 H.sub.5 " 273 " " "             ##STR212##                                                                      " 274 " " "                                                                     ##STR213##                                                                      " 275 " "                                                                       ##STR214##                                                                      ##STR215##                                                                      " 276 " " NH(CH.sub.2).sub.4 OH NHC.sub.2 H.sub.4 OCH.sub.3 " 277 " "          NH(CH.sub.2).sub.6 OH " " 278 " " NH(CH.sub.2).sub.3 O(CH.sub.2).sub.4          OH " " 279 " " NHC.sub.2 H.sub.4                                                 OH                                                                             ##STR216##                                                                       " 280 " " "                                                                     ##STR217##                                                                      " 281 "                                                                         ##STR218##                                                                      " NHC.sub.2 H.sub.4 OCH.sub.3 " 282 " CH.sub.3 NHC.sub.2 H.sub.4               OCH.sub.3 NHC.sub.2 H.sub.4 C.sub.6 H.sub.4 SO.sub. 3 H orange 283 "            CH.sub.3 NHC.sub.2 H.sub.4 C.sub.6 H.sub.4 SO.sub.3                              H " " 284 "                                                                    ##STR219##                                                                       " " " 285 " CH.sub.2 C.sub.6 H.sub.4 SO.sub.3 H NHC.sub.2 H.sub.4              OCH.sub.3 NHC.sub.2 H.sub.4 OCH.sub.3 " 286 " " NHCH.sub.2 C.sub.6              H.sub.4 SO.sub.3 H NH(CH.sub.2).sub.3 OCH.sub.3 " 287 " N(C.sub.2               H.sub.5).sub.2 H NHC.sub.2 H.sub.4 C.sub.6 H.sub.4 SO.sub.3 H " 288 " "         CH.sub.3 " " 289 "                                                               ##STR220##                                                                      " NHC.sub.6 H.sub.4 SO.sub.3                                                    H " 290                                                                        ##STR221##                                                                       ##STR222##                                                                      NHC.sub.2 H.sub.4 OH NHC.sub.2 H.sub.4 OH yellowish red   291 "                N(C.sub.2 H.sub.5).sub.2 CH.sub.3 NHC.sub.2 H.sub.4 C.sub.6 H.sub.4             SO.sub.3                                                                         H orange 292                                                                   ##STR223##                                                                       ##STR224##                                                                      NHC.sub.2 H.sub.4 OH NHCH.sub.2 C.sub.6 H.sub.4 SO.sub.3 H yellowish           red                                                                               293                                                                           ##STR225##                                                                       " " " " 294                                                                     ##STR226##                                                                      " " NHCH.sub.2 C.sub.6                                                          H.sub.5 yellow 295                                                             ##STR227##                                                                       " " " " 296                                                                     ##STR228##                                                                      " " " " 297 " " "                                                               ##STR229##                                                                      " 298 "                                                                         ##STR230##                                                                      CH.sub.3 NHCH.sub.2 C.sub.6 H.sub.4 SO.sub.3                                    H " 299                                                                        ##STR231##                                                                       ##STR232##                                                                      NHC.sub.3 H.sub.7 NHC.sub.3 H.sub.7 " 300 " " NHC.sub.2 H.sub.4 OH             NHC.sub.4                                                                        H.sub.9 " 301 "                                                                ##STR233##                                                                       NH(CH.sub.2).sub.3 OH NH(CH.sub.2).sub.3 OC.sub.3 H.sub.7 (i) " 302 "          CH.sub.3 " NHC.sub.2 H.sub.4 C.sub.6 H.sub.4 SO.sub.3                            H " 303 "                                                                      ##STR234##                                                                       " NH(CH.sub.2).sub.3                                                            OH " 304 "                                                                     ##STR235##                                                                       CH.sub.3 NHCH.sub.2 C.sub.6 H.sub.4 SO.sub.3                                    H " 305                                                                        ##STR236##                                                                       ##STR237##                                                                      NHC.sub.2 H.sub.4 OH NHC.sub.4                                                  H.sub.9 " 306 "                                                                ##STR238##                                                                       CH.sub.3 NHCH.sub.2 C.sub.6 H.sub.4 SO.sub.3                                    H " 307                                                                        ##STR239##                                                                       ##STR240##                                                                      NHC.sub.2 H.sub.4 OH NHC.sub.4                                                  H.sub.9 orange 308                                                             ##STR241##                                                                       " " NHC.sub.2 H.sub.4 C.sub.6                                                   H.sub.5 reddishorange 309 " " NH(CH.sub.2).sub.3                                OCH.sub.3 NH(CH.sub.2).sub.3 OCH.sub.3 " 310 " N(C.sub.4 H.sub.9).sub.2        CH.sub.3 NHC.sub.2 H.sub.4 C.sub.6 H.sub.4 So.sub.3 H orange 311                 ##STR242##                                                                      ##STR243##                                                                      NHC.sub.2 H.sub.4 OH NH(CH.sub.2).sub.3 OCH.sub.2 C.sub.6 H.sub.4              SO.sub.3                                                                         H " 312 "                                                                      ##STR244##                                                                       " " " 313                                                                       ##STR245##                                                                      ##STR246##                                                                      " NHC.sub.6                                                                     H.sub.13 red 314 " " "                                                         ##STR247##                                                                       " 315 "                                                                         ##STR248##                                                                      " NHC.sub.2 H.sub.4 C.sub.6 H.sub.4 SO.sub.3                                    H " 316 "                                                                      ##STR249##                                                                       CH.sub.3 " reddishorange 317 "                                                  ##STR250##                                                                      CH.sub.3 " " 318                                                                ##STR251##                                                                      ##STR252##                                                                      NH(CH.sub.2).sub.3 OCH.sub.3 NH(CH.sub.2).sub.3 OCH.sub.3 yellowish red          319 " " NHC.sub.2 H.sub.4 OH NHC.sub.2 H.sub.4 OCH.sub.3 " 320                 ##STR253##                                                                      " " NHC.sub.2 H.sub.4                                                           OH red                                                                   

EXAMPLE 321

14.9 parts of the coupling product from 4-aminoazobenzene and 2-phenyl-4-β-hydroxyethylamino-6-β-methoxyethylaminopyrimidine is introduced while cooling into 200 parts of 96% sulfuric acid. The mixture is stirred for several hours at room temperature and then the solution is poured into an amount of ice-water enough to prevent the temperature rising above 10° C. The precipitated dye of the probable formula: ##STR254## is filtered off, washed with water, dissolved in dilute caustic soda solution, filtered and precipitated as the sodium salt with sodium chloride. Conventional processing gives a reddish brown powder which colors synthetic polyamide material fast yellowish red hues.

EXAMPLE 322

A solution of 13.4 parts of the coupling product from 4-amino-2-methyl-5-methoxy-4'-β-hydroxyethoxyazobenzene and 2-phenyl-4,6-bis-γ-ethoxypropylaminopyrimidine in 150 parts of 96% sulfuric acid is stirred for twenty-four hours at room temperature. Then the mixture is added to so much ice that the temperature does not rise above 10° C. The dye of the formula: ##STR255## is thus precipitated. It is isolated, dissolved in dilute caustic soda solution and reprecipitated as the sodium salt. At the end of processing a dark brown powder is obtained which gives full red hues having good fastnesses on polyamide cloth.

The dyes of the following Table are similarly prepare according to the methods expressly described in Example 1 to 4, 176 to 179 and 321 to 322:

                                                                                      Ex.      No. DK X.sup.1 X.sup.2 X.sup.3 Hue                                            323                                                                      ##STR256##                                                                      ##STR257##                                                                      NH(CH.sub.2).sub.5 COOH NHC.sub.2 H.sub.4                                       OCH.sub.3 orange 324                                                           ##STR258##                                                                         "   "   "   " 325   "   " NHC.sub.2 H.sub.4 OCCC.sub.2 H.sub.4 COOH          "                                                                                " 326                                                                          ##STR259##                                                                         " NHC.sub.2 H.sub.4 OH NHC.sub.2 H.sub.4 C.sub.6                              H.sub.5 reddishyellow 327                                                       "                                                                              ##STR260##                                                                       NH.sub.2 NHC.sub.2 H.sub.4 OH yellow 328   "   " NHC.sub.2 H.sub.5   "         reddish      yellow 329                                                          "                                                                              ##STR261##                                                                       CH.sub.3 NHC.sub.2 H.sub.4                                                      OCH.sub.3 yellow 330                                                           ##STR262##                                                                       ##STR263##                                                                      NHC.sub.2 H.sub.4 OSO.sub.3 H NH(CH.sub.2)OCH.sub.3 reddishyellow 331           ##STR264##                                                                      ##STR265##                                                                      NH(CH.sub.2).sub.5 COOH NHC.sub.2 H.sub.4 OCH.sub.3 reddishyellow 332           ##STR266##                                                                      ##STR267##                                                                      CH.sub.3 NH(CH.sub.2).sub.3 O(CH.sub.2).sub.4 OSO.sub.3 H orange 333            ##STR268##                                                                      ##STR269##                                                                      NHC.sub.2 H.sub.4 OSO.sub.3 H NHCH.sub.2 C.sub.6 H.sub.4 SO.sub.3 H            yellow 334   "   " NHC.sub.2 H.sub.4 SO.sub.3 H NH(CH.sub.2).sub.3              OCH.sub.3   " 335                                                                "                                                                              ##STR270##                                                                       NHC.sub.2 H.sub.4 OH NHC.sub.6 H.sub.4 SO.sub.3 H   " 336   "   "              NHC.sub.2 H.sub.4 OSO.sub.3 H NHC.sub.6 H.sub.5   " 337   "   "   "              ##STR271##                                                                        " 338                                                                         "                                                                              ##STR272##                                                                       NH(C.sub.2 H.sub.4 O).sub.2 SO.sub.3 H NH(C.sub.2 H.sub.4 O).sub.2             SO.sub.3 H                                                                       " 339                                                                          ##STR273##                                                                       ##STR274##                                                                      NHC.sub.2 H.sub.4 OCOCH.sub.3 NH(CH.sub.2).sub.3 OCH.sub.3   " 340              ##STR275##                                                                      ##STR276##                                                                      NHC.sub.2 H.sub.4 OSO.sub.3 H NH(CH.sub.2).sub.3 OCH.sub.3 orange 341          "                                                                                ##STR277##                                                                      NHC.sub.2 H.sub.4 SO.sub.3 H   "                                                " 342                                                                          ##STR278##                                                                         " NHC.sub.2 H.sub.4 OSO.sub.3 H NHC.sub.2 H.sub.4 OSO.sub.3 H   " 343          " N(C.sub.2 H.sub.5).sub.2 CH.sub.3 NH(CH.sub.2).sub.3 OC.sub.2               H.sub.4 OC.sub.6 H.sub.4 SO.sub.3                                                H yellow 344                                                                   ##STR279##                                                                       ##STR280##                                                                      NHC.sub.2 H.sub.4 OSO.sub.3 H NHC.sub.2 H.sub.4 OSO.sub. 3 H   " 345            ##STR281##                                                                        " NHSO.sub.3 H NHC.sub.2 H.sub.4 OCH.sub.3 orange 346   "   "                NHC.sub.2 H.sub.4 SO.sub.3 H NH(CH.sub.2).sub.3 OCH.sub.3 reddish               orange 347                                                                       "                                                                              ##STR282##                                                                       NHC.sub.2 H.sub.4 OSO.sub.3                                                     H                                                                              ##STR283##                                                                         " 348   "   "                                                                 "                                                                              ##STR284##                                                                         " 349   "   " NH(CH.sub.2).sub.6 OSO.sub.3 H NHC.sub.2 H.sub.4               OCH.sub.3   " 350   " N(C.sub.2 H.sub.5).sub.2 CH.sub.3 NHC.sub.2               H.sub.4 SO.sub.3 H                                                               " 351                                                                          ##STR285##                                                                       ##STR286##                                                                      NHC.sub.2 H.sub. 4 OSO.sub.3 H NHC.sub.2 H.sub.4 OSO.sub.3                      H yellowishred 352                                                              ##STR287##                                                                        "   " NHC.sub.4 H.sub.9 yellow 353                                            "                                                                              ##STR288##                                                                       NH(CH.sub.2).sub.3 OSO.sub.3 H NH(CH.sub.2).sub.3 OSO.sub.3 H   " 354           ##STR289##                                                                      ##STR290##                                                                      NHC.sub.2 H.sub.4 OSO.sub.3 H NHC.sub.4 H.sub.9                                 " 355                                                                          ##STR291##                                                                         "   "                                                                         " orange 356                                                                   ##STR292##                                                                         "   " NH(CH.sub.2).sub.3 OCH.sub.2 C.sub.6 H.sub.5                            " 357                                                                          ##STR293##                                                                         " NHC.sub.2 H.sub.4 SO.sub.3 H NH(CH.sub.2).sub.3 OCH.sub.3 red 358           ##STR294##                                                                        " NHC.sub.2 H.sub.4 OCH.sub.3 NHC.sub.2 H.sub.4 OCH.sub.3   " 359             ##STR295##                                                                      ##STR296##                                                                      NH(CH.sub.2).sub.3 OH NH(CH.sub.2).sub.3 OH yellowishred 360   "                ##STR297##                                                                        "   "   " 361                                                                 "                                                                              ##STR298##                                                                       NHC.sub.2 H.sub.4 OH NHC.sub.2 H.sub.4                                          OH reddishorange 362                                                           ##STR299##                                                                       ##STR300##                                                                      NH(CH.sub.2).sub.3 OCH.sub.3 NH(CH.sub.2).sub.3 OCH.sub.3violet 363             ##STR301##                                                                      ##STR302##                                                                      NHC.sub.2 H.sub.4 OHNHC.sub.2 H.sub.4                                           OH red 364                                                                     ##STR303##                                                                       ##STR304##                                                                     NHC.sub.2 H.sub.5 NHC.sub.2                                                      H.sub.5 yellow 365                                                             ##STR305##                                                                       N(C.sub.2 H.sub.5).sub.2 CH.sub.3 NH(C.sub.2 H.sub.4 O).sub.2 H " 366           ##STR306##                                                                      N(CH.sub.3).sub.2 CH.sub.3 NHC.sub.2 H.sub.4 C.sub.6 H.sub.5   " 367            ##STR307##                                                                      N(C.sub.4 H.sub.9).sub.2 CH.sub.3 NHC.sub.2 H.sub.4 C.sub.6 H.sub.4            SO.sub.3 H                                                                       " 368                                                                          ##STR308##                                                                       ##STR309##                                                                     CH.sub.3 NHC.sub.3 H.sub.6 OH                                                    " 369                                                                          ##STR310##                                                                       ##STR311##                                                                      NHC.sub.3 H.sub.6 OCH.sub.3 NHC.sub.3 H.sub.6 OCH.sub.3   " 370                 ##STR312##                                                                      ##STR313##                                                                     NH(C.sub.2 H.sub.4 O).sub.2 H NH(C.sub.2 H.sub.4 O).sub.2 H   " 371              ##STR314##                                                                     N(C.sub.4 H.sub.9).sub.2 CH.sub.3 NHC.sub.2 H.sub.4 C.sub.6 H.sub.4             SO.sub.3 H                                                                       " 372                                                                          ##STR315##                                                                       ##STR316##                                                                     NH.sub.2 NHC.sub.3 H.sub.6                                                       OCH.sub.3 yellowishred 373                                                     ##STR317##                                                                       ##STR318##                                                                     NH(C.sub.2 H.sub.4 O).sub.2 H NH(C.sub.2 H.sub.4 O).sub.2 H   " 374              ##STR319##                                                                      ##STR320##                                                                     NH.sub.2 NHC.sub.3 H.sub.6 OCH.sub.3                                             " 375                                                                          ##STR321##                                                                      N(C.sub.2 H.sub.5).sub.2 CH.sub.3 NHC.sub.2 H.sub.4 C.sub.6 H.sub.5   "         376                                                                              ##STR322##                                                                     N(C.sub.3 H.sub.7).sub.2CH.sub.3 NHC.sub.6 H.sub.5                               " 377                                                                          ##STR323##                                                                       ##STR324##                                                                      NHC.sub.2 H.sub.4 OCH.sub.3 NHC.sub.2 H.sub.4 OCH.sub.3   " 378                 ##STR325##                                                                      ##STR326##                                                                      NH(C.sub.2 H.sub.4 O).sub.2 H NHC.sub.2 H.sub.4 C.sub.6 H.sub.4                SO.sub.3                                                                         H red 379                                                                      ##STR327##                                                                       ##STR328##                                                                      NHC.sub.2 H.sub.5 NHC.sub.2 H.sub.5                                             " 380                                                                          ##STR329##                                                                       ##STR330##                                                                      NHC.sub.3 H.sub.6 OH NHC.sub. 3 H.sub.6 OH                                      " 381                                                                          ##STR331##                                                                       ##STR332##                                                                      NH(C.sub.2 H.sub.4 O).sub.2 H NH(C.sub.2 H.sub.4 O).sub.2 H   " 382             ##STR333##                                                                      ##STR334##                                                                      NHC.sub.2 H.sub.4 OCH.sub.3 NHC.sub.2 H.sub.4 OCH.sub.3   " 383                 ##STR335##                                                                      ##STR336##                                                                      NHC.sub.3 H.sub.6 OCH.sub.3 NHC.sub.3 H.sub.6 OCH.sub.3   " 384                 ##STR337##                                                                      ##STR338##                                                                      NHC.sub.2 H.sub.5NHC.sub.2 H.sub.5                                              " 385                                                                          ##STR339##                                                                       ##STR340##                                                                      NHC.sub.3 H.sub.6 OH NHC.sub.3 H.sub.6 OH                                       " 386                                                                          ##STR341##                                                                       ##STR342##                                                                      NH(C.sub.2 H.sub.4 O).sub.2 H NH(C.sub.2 H.sub.4 O).sub.2 H   " 387             ##STR343##                                                                      ##STR344##                                                                      NHC.sub.6 H.sub.5NHC.sub.2 H.sub.4                                              OH orange 388                                                                  ##STR345##                                                                       N(C.sub.2                                                                       H.sub.5).sub.2 CH.sub.3                                                        ##STR346##                                                                       yellow 389                                                                      ##STR347##                                                                      ##STR348##                                                                     CH.sub.3 NH(CH.sub.2).sub.3 O(CH.sub.2).sub.2 OC.sub.6 H.sub.4 SO.sub.3         H                                                                                " 390                                                                          ##STR349##                                                                       ##STR350##                                                                      NHC.sub.2 H.sub.5 NHC.sub.2 H.sub.5                                             " 391                                                                          ##STR351##                                                                       N(CH.sub.3).sub.2 CH.sub.3                                                      ##STR352##                                                                        " 392    "   "   " NHCH.sub.2 C.sub.6 H.sub.4 SO.sub.3 H   " 393    "          "   " NH(CH.sub.2).sub.3 OCH.sub.2 C.sub.6 H.sub.4 SO.sub.3 H   " 394          ##STR353##                                                                      N(CH.sub.3).sub.2 CH.sub.3                                                      ##STR354##                                                                      " 395                                                                          ##STR355##                                                                       ##STR356##                                                                      NHCH.sub.2 C.sub.6 H.sub.4 SO.sub.3 H NHCH.sub.2 C.sub.6 H.sub.4               SO.sub.3 H   " 396    "    " NHC.sub.2 H.sub.4 C.sub.6 H.sub.4 SO.sub.3         H NHC.sub.2 H.sub.4 C.sub.6 H.sub.4 SO.sub.3 H                                   " 397                                                                          ##STR357##                                                                         "   "   "                                                                     " 398                                                                          ##STR358##                                                                         "   "                                                                         " yellowish red 399                                                            ##STR359##                                                                         "    "   "                                                                    " 400                                                                          ##STR360##                                                                         "   "   " red 401   "   " NHCH.sub.2 C.sub.6 H.sub.4 SO.sub.3 H              NHCH.sub.2 C.sub.6 H.sub.4 SO.sub.3 H                                            " 402                                                                          ##STR361##                                                                         "   "   "   " 403    "   " NH(C.sub.2 H.sub.4 O).sub.2 H NHC.sub.2           H.sub.4 C.sub.6 H.sub.4 SO.sub.3 H   " 404   "   " NHC.sub.2 H.sub.4            C.sub.6 H.sub.4 SO.sub.3 H   "   " 405   "   " NH(CH.sub.2).sub.3               OCH.sub.2 C.sub.6 H.sub.4 SO.sub.3 H NH(CH.sub.2).sub.3 OCH.sub.2               C.sub.6 H.sub.4 SO.sub.3 H   " 406   "   " NH(CH.sub.2).sub.3                    O(CH.sub.2).sub.2 OC.sub.6 H.sub.4 SO.sub.3 H NH(CH.sub.2).sub.3               O(CH.sub.2).sub.2 OC.sub.6 H.sub.4 SO.sub.3 H                                    "                                                                         

We claim:
 1. A dye of the formula: ##STR362## in which D is selected from the group consisting of(1) phenyl substituted by chloro; bromo; methyl; ethyl; trifluoromethyl; cyano; methylsulfonyl; ethylsulfonyl; phenylsulfonyl; C₁ - to C₄ -alkoxycarbonyl; carbamoyl; sulfamoyl; sulfamoyl substituted at the nitrogen once or twice by C₁ - to C₂ -alkyl, β-hydroxyethyl, γ-hydroxypropyl, β-methoxyethyl or γ-methoxypropyl; hydroxysulfonyl; SO₂ NHC₂ H₄ SO₃ H; or 6-methyl-7-sulfo-2-benzthiazolyl; (2) phenylazophenyl; (3) phenylazophenyl substituted by hydroxy, methyl, methoxy, ethoxy, hydroxysulfonyl or --OC₂ H₄ --O--SO₃ H; (4) 3- or 4-phthalimidyl; and (5) 3- or 4-phthalimidyl substituted at the nitrogen by C₁ - to C₄ -alkyl, β-hydroxyethyl, β-methoxyethyl, γ-hydroxypropyl, β-hydroxyethoxyethyl, benzyl, phenylethyl, sulfobenzyl, sulfophenylethyl, phenyl or phenyl substituted by methyl or hydroxysulfonyl;one Z is ##STR363## and the other Z is hydrogen; C₁ - to C₃ -alkyl; cyclohexyl; benzyl; sulfobenzyl; phenylethyl; sulfophenylethyl; phenyl; or phenyl substituted by methyl, chloro, methoxy, ethoxy or hydroxysulfonyl; Z¹ is hydrogen; C₁ - to C₈ -alkyl; C₂ - to C₆ -alkyl substituted by hydroxy, methoxy, ethoxy or cyano; cyclohexyl; norbornyl; benzyl; sulfobenzyl; phenylethyl; sulfophenylethyl; phenylpropyl; sulfophenylpropyl; phenyl; phenyl substituted by methyl, methoxy, ethoxy, chloro or hydroxysulfonyl; sulfoethyl; (CH₂)₃ OC₆ H₅ ; (CH₂)₃ OC₆ H₄ SO₃ H; (CH₂)₃ OCH₂ C₆ H₅ ; (CH₂)₃ OCH₂ C₆ H₄ SO₃ H; C₂ H₄ OC₂ H₄ OH; (CH₂)₃ OC₂ H₄ OZ⁵ ; or (CH₂)₃ O(CH₂)₄ OH; Z³ has the meanings given for Z¹ ; Z² is hydrogen or C₁ - to C₄ -alkyl; Z¹ and Z² together with the nitrogen are pyrrolidino, piperidino or morpholino; and Z⁵ is C₁ - to C₄ -alkyl, benzyl, sulfobenzyl, phenyl or sulfophenyl, with the proviso that the dye contains a total of 1, 2 or 3 sulfonic acid groups.
 2. A dye according to claim 1 having the formula ##STR364## in which Z is hydrogen; C₁ - to C₃ -alkyl; cyclohexyl; benzyl; sulfobenzyl; phenylethyl; sulfophenylethyl, phenyl; or phenyl substituted by methyl, chloro, methoxy, ethoxy or hydroxysulfonyl; and D, Z¹ and Z³ have the meanings given for claim
 1. 3. A dye according to claim 1 having the formula ##STR365## in which Z is hydrogen; C₁ - to C₃ -alkyl; cyclohexyl; benzyl; sulfobenzyl; phenylethyl; sulfophenylethyl; phenyl; or phenyl substituted by methyl, chloro, methoxy, ethoxy or hydroxysulfonyl; and D, Z¹, Z² and Z³ have the meanings given for claim
 1. 4. A dye according to claim 1 having the formula ##STR366## in which D¹ is a radical of the formula: ##STR367## p is zero or 1; Y is hydrogen, cyano, chloro, bromo, methylsulfonyl, ethylsulfonyl, phenylsulfonyl, methoxycarbonyl, ethoxycarbonyl or SO₃ H;Y¹ is hydrogen, chloro, bromo or SO₃ H; Y² is hydrogen, chloro, bromo, methyl, methylsulfonyl, methoxycarbonyl, ethoxycarbonyl, 6-methyl-7-sulfo-2-benzothiazolyl or SO₃ H; X is hydrogen, methyl, hydroxy, methoxy, ethoxy or SO₃ H; X¹ is hydrogen, methyl or SO₃ H; X² is hydrogen or methyl; T is hydrogen, β-hydroxyethyl, γ-hydroxypropyl, β-methoxyethyl, benzyl, phenyl or methylphenyl; and Z and Z³ have the meanings given for claim
 1. 5. A dye according to the formula in claim 2 in whichZ is methyl, ethyl, propyl, benzyl, sulfobenzyl, phenyl or phenyl bearing methyl or methoxy, Z¹ is C₁ to C₄ -alkyl; C₂ - or C₃ -alkyl bearing hydroxy, methoxy or ethoxy as substituent; benzyl; sulfobenzyl; phenylethyl; sulfophenylethyl; phenylpropyl; sulfophenylpropyl; phenyl; phenyl bearing methyl, methoxy or hydroxysulfonyl as substituent; sulfoethyl; CH₂ CH₂ OCH₂ --CH₂ OH; (CH₂)₃ O(CH₂)₄ OH; (CH₂)₃ OCH₂ C₆ H₅ ; (CH₂)₃ OCH₂ C₆ H₄ SO₃ H; (CH₂)₃ O(CH₂)₂ OC₆ H₅ ; or (CH₂)₃ O(CH₂)₂ OC₆ H₄ SO₃ H; Z³ is hydrogen or Z¹ ; and D has the meanings given for claim
 2. 6. A dye according to the formula in claim 3 in whichZ is methyl, ethyl, propyl or phenyl; Z¹ is C₁ - to C₄ -alkyl, cyclohexyl, benzyl, sulfobenzyl, phenylethyl or sulfophenylethyl; Z² is hydrogen or C₁ - to C₄ -alkyl; Z¹ and Z² together with the nitrogen are pyrrolidino, piperidino or morpholino; Z³ is C₁ to C₄ -alkyl; C₂ - or C₃ -alkyl bearing hydroxy, methoxy or ethoxy as substituent; benzyl; sulfobenzyl; phenylethyl; sulfophenylethyl; phenylpropyl, sulfophenylpropyl; phenyl; phenyl bearing methyl, methoxy or hydroxysulfonyl as substituent; sulfoethyl; CH₂ CH₂ OCH₂ CH₂ OH, (CH₂)₃ OCH₂ C₆ H₅, (CH₂)₃ OCH₂ C₆ H₄ SO₃ H; (CH₂)₃ O(CH₂)₂ OC₆ H₅ ; (CH₂)₃ O(CH₂)₂ OC₆ H₄ SO₃ H; or (CH₂)₃ O(CH₂)₄ OH; and D has the meanings given for claim
 3. 7. The dye according to claim 1 having the formula ##STR368##
 8. The dye according to claim 1 having the formula ##STR369##
 9. The dye according to claim 1 having the formula ##STR370##
 10. The dye according to claim 1 having the formula ##STR371##
 11. The dye according to claim 1 having the formula ##STR372##
 12. The dye according to claim 1 having the formula ##STR373## 